CN116745084A - Cellulose ester compositions and articles made therefrom - Google Patents

Abstract

A polymer composition comprising cellulose acetate in combination with one or more plasticizers and one or more biodegradable fillers. Biodegradable fillers may include monosaccharides, polysaccharides, their esters, and mixtures thereof. The polymer composition is formulated to have properties similar to petroleum-based polymers used to produce, for example, disposable biodegradable articles.

Description

Cellulose ester compositions and articles made therefrom

RELATED APPLICATIONS

The present application is based on and claims priority from U.S. provisional patent application Ser. No. 63/116,464, filed 11/20/2020, which is incorporated herein by reference.

Background

Global plastic production continues to increase each year. More than half of the annual production of plastics is used to produce plastic bottles, containers, straws and other disposable items. For example, more than 1 million disposable plastic pipettes are produced and used annually.

Disposable plastic products, including plastic beverage bottles and straws, are generally not recycled and ultimately enter landfills. In addition, many of these items are not properly handled and eventually enter rivers, lakes, and oceans around the world. In fact, plastic waste tends to collect and concentrate in the ocean in some parts of the world due to ocean currents and product buoyancy.

Plastic waste can be harmful to ecosystems and animals, including marine organisms and birds. For example, plastic waste breaks down very slowly into smaller and smaller pieces that can be ingested by aquatic organisms and fish.

In view of this, the person skilled in the art has tried to produce plastic articles made of biodegradable polymers. However, many biodegradable polymers lack the physical properties and characteristics of conventional polymers such as polypropylene and/or polyethylene terephthalate.

Cellulose esters have been proposed in the past as alternatives to some petroleum-based polymers or plastics. For example, cellulose esters are generally considered environmentally friendly polymers because they are recyclable, degradable, and derived from renewable resources such as wood pulp. However, problems have been encountered in melt processing cellulose ester polymers (e.g., cellulose acetate polymers). In addition, articles made from cellulose acetate polymers have various disadvantages due to the mechanical properties of the polymers.

In view of this, there is a need for biodegradable polymer compositions that have properties similar to petroleum-based polymers and that can be melt processed to form various three-dimensional articles. There is also a need for cellulose acetate polymer compositions having enhanced biodegradability and/or improved mechanical properties.

Disclosure of Invention

In general, the present disclosure is directed to polymer compositions comprising a cellulose acetate polymer in combination with at least one plasticizer and a biodegradable filler. The biodegradable filler may be, for example, a monosaccharide ester, a polysaccharide ester, or a mixture thereof. Biodegradable fillers may improve the biodegradable properties of cellulose acetate polymers and/or improve the mechanical properties of articles made from the polymer compositions.

The polymer compositions of the present disclosure may be used in, for example, injection molding processes, extrusion molding processes, or other melt processing systems. The biodegradable filler may be added during the production of the article. Alternatively, the biodegradable filler may be combined with the cellulose acetate polymer during extrusion molding and formed into pellets, which are subsequently used to form various polymer articles.

In one aspect, the polymer composition comprises a cellulose ester polymer (e.g., a cellulose acetate polymer) in combination with at least one plasticizer and at least one biodegradable filler. The biodegradable filler may be a monosaccharide, a monosaccharide ester, a polysaccharide ester, or a combination thereof. The biodegradable filler may be in the form of fibers, powders, granules, mixtures thereof, and the like. The biodegradable filler may also be in the form of a solution or suspension when combined with the cellulose ester polymer.

In one aspect, the biodegradable filler may include dextran, starch, hydrolyzed starch, modified hydrolyzed starch, alpha-1, 3-glucan (including glucan polymers), or mixtures thereof. In another aspect, the biodegradable filler may comprise alpha-cellulose, bast fibers such as hemp, hardwood fibers, softwood fibers, sisal fibers, viscose fibers or mixtures thereof. In yet another aspect, the biodegradable filler may comprise an engineered polysaccharide (engineered polysaccharide).

One or more biodegradable fillers as described above are typically present in the polymer composition in an amount of about 0.1wt% to about 75 wt%. For example, the one or more biodegradable fillers may be present in the polymer composition in an amount of about 3wt% to about 50wt%, such as in an amount of 3wt% to about 25 wt%.

The cellulose acetate may be present in the composition in an amount of about 15wt% to about 85wt%, such as about 55wt% to about 80 wt%. Cellulose acetate may consist essentially of cellulose diacetate. For example, the cellulose acetate may comprise cellulose diacetate in an amount of greater than about 90wt%, such as in an amount of greater than about 95 wt%. In one aspect, the cellulose ester polymer or cellulose acetate may have a degree of substitution of about 1.3 to about 2.9. In another aspect, the one or more plasticizers may be present in the polymer composition in an amount of about 8wt% to about 40wt%, such as about 12wt% to about 20 wt%. In one aspect, the one or more plasticizers may be present in the polymer composition in an amount of about 19wt% or less, such as about 17wt% or less, such as about 15wt% or less.

Generally, any suitable plasticizer may be incorporated into the polymer composition. Plasticizers that may be used include glyceryl triacetate, tri (chloroisopropyl) phosphate, tri (2-chloro-1-methylethyl) phosphate, glycerin, glyceryl monoacetate, glyceryl diacetate, triethyl citrate, acetyl triethyl citrate, or mixtures thereof.

The polymer composition may also contain various other additives and ingredients. For example, the polymer composition may include acid scavengers, antioxidants, colorants, and the like.

The polymer compositions formulated according to the present disclosure can be used to produce injection molded or extruded articles. In one embodiment, the polymer composition may comprise foam or form foam during the production of the article.

Polymeric articles that may be made according to the present disclosure include drinking straws, beverage holders, automotive parts, knobs, door handles, lids, packaging materials, cutlery, household electrical appliance parts, containers, and any other suitable disposable product. For example, the present disclosure is also directed to a straw comprising an elongate tubular member defining a channel from a first end to an opposing second end. The straw is formed from the polymer composition described above.

Other features and aspects of the present disclosure will be discussed in more detail below.

Drawings

A full and enabling disclosure of the present disclosure, including the enabling disclosure thereof, is set forth more particularly in the remainder of the specification, including reference to the accompanying figures, in which:

FIG. 1 is a perspective view of a straw that may be made in accordance with the present disclosure;

FIG. 2 is a cross-sectional view of a beverage holder that may be made in accordance with the present disclosure;

FIG. 3 is a side view of one embodiment of a beverage can that can be made in accordance with the present disclosure;

FIG. 4 is a cross-sectional view of a beverage bottle that may be made in accordance with the present disclosure;

FIG. 5 is a perspective view of an interior of an automobile showing various articles that may be made according to the present disclosure;

FIG. 6 is a perspective view of cutlery that may be made in accordance with the present disclosure;

FIG. 7 is a perspective view of a cover that may be made in accordance with the present disclosure; and

fig. 8 is a perspective view of a container that can be made in accordance with the present disclosure.

In the present specification and drawings, repeated use of reference characters is intended to represent the same or analogous features or elements of the disclosure.

Detailed Description

It is to be understood by one of ordinary skill in the art that the present description is illustrative of exemplary embodiments only and is not intended to limit the broader aspects of the present disclosure.

In general, the present disclosure is directed to polymer compositions comprising a combination of a cellulose ester polymer and other components that improve the melt processability and/or physical properties of cellulose acetate. According to the present disclosure, cellulose acetate is combined with one or more plasticizers and one or more biodegradable fillers. The biodegradable filler may be, for example, a monosaccharide ester, a polysaccharide ester, or a mixture thereof. In one aspect, one or more biodegradable fillers having a greater degradation rate than the cellulose ester polymer are selected. In this way, degradation of polymeric articles made from the polymeric composition after use can be significantly accelerated.

Furthermore, polymer compositions formulated according to the present disclosure may also have significantly improved mechanical properties. The polymer composition can be used to form all of the different types of products using any suitable molding technique, such as extrusion molding, injection molding, rotational molding, gel processing, and the like.

In general, any suitable cellulose ester polymer may be incorporated into the polymer compositions of the present disclosure. In one aspect, the cellulose ester polymer is cellulose acetate.

Cellulose acetate may be formed by activating cellulose with acetic acid followed by cellulose esterification. Cellulose may be obtained from various types of cellulosic materials including, but not limited to, biomass of plant origin, corn stover, sugar cane stalks, bagasse and sugar cane residues, rice and wheat straw, agricultural grasses, hardwood pulp, softwood pulp, cotton linters, switchgrass, bagasse, herbaceous plants, recycled paper, waste paper, wood chips, pulp and paper waste, waste wood, meta-lumber, willow, poplar, perennial grasses (e.g., grasses of Miscanthus), bacterial cellulose, seed hulls (e.g., soybean), corn stalks, chaff and other forms of wood, bamboo, bean hulls, bast fibers (e.g., kenaf, hemp, jute and flax), agricultural residue products, agricultural waste, livestock waste, microorganisms, algal cellulose, seaweed, and other materials that are approximately or ultimately derived from plants. Such cellulosic raw materials are preferably processed in the form of pellets, chips, trimmings, flakes, milled fibers, powders or other forms, making them suitable for further purification.

In some embodiments, cellulose esters suitable for use in producing the compositions of the present disclosure may have ester substituents including, but not limited to, C ₁ -C ₂₀ Aliphatic esters (e.g., acetate, propionate, or butyrate), functionalized C ₁ -C ₂₀ Aliphatic esters (e.g., succinic esters, glutaric esters, maleic esters), aromatic esters (e.g., benzoic esters or phthalic esters), substituted aromatic esters, and the like, any derivatives thereof, and any combination thereof.

The cellulose acetate used in the composition may be a diacetyl cellulose or a triacetyl cellulose. In one embodiment, the cellulose acetate consists essentially of cellulose diacetate. For example, the cellulose acetate may comprise less than 1wt% cellulose triacetate, such as less than about 0.5wt% cellulose triacetate. The diacetyl cellulose may comprise greater than 90wt% of the cellulose acetate, such as greater than about 95wt%, such as greater than about 98wt%, such as greater than about 99wt% of the cellulose acetate.

Typically, the cellulose acetate may have a molecular weight of greater than about 10,000, such as greater than about 20,000, such as greater than about 30,000, such as greater than about 40,000, such as greater than about 50,000. The molecular weight of the cellulose acetate is typically less than about 300,000, such as less than about 250,000, such as less than about 200,000, such as less than about 150,000, such as less than about 100,000, such as less than about 90,000, such as less than about 70,000, such as less than about 50,000. The above molecular weight refers to a number average molecular weight. Molecular weight can be determined using gel permeation chromatography using polystyrene equivalent or standard.

Biodegradation of cellulose ester polymers depends on various factors, including the degree of substitution. The degree of substitution of the cellulose ester can be measured using, for example, ASTM test 871-96 (2010). The cellulose acetate polymer included in the polymer composition typically has a degree of substitution of greater than about 1.3, such as greater than about 1.5, such as greater than about 1.7, such as greater than about 1.9, such as greater than about 2.1, such as greater than about 2.3. The degree of substitution is generally less than about 2.9, such as less than about 2.7, such as less than about 2.6, such as less than about 2.4.

The cellulose ester polymer or cellulose acetate may have an inherent viscosity generally greater than about 0.5dL/g, such as greater than about 0.8dL/g, such as greater than about 1dL/g, such as greater than about 1.2dL/g, such as greater than about 1.4dL/g, such as greater than about 1.6 dL/g. The inherent viscosity is typically less than about 2dL/g, such as less than about 1.8dL/g, such as less than about 1.7dL/g, such as less than about 1.65dL/g. Intrinsic viscosity can be measured by: a solution of 0.20g/dL cellulose ester was formed in 98/2wt/wt acetone/water and the flow times of the solution and solvent were measured using a #25Cannon-Ubbelohde viscometer at 30 ℃. The modified Baker-Philipopff equation can then be used to determine the intrinsic viscosity ("IV"), equation 1 for this solvent system.

Wherein the method comprises the steps oft ₁ Solution (with)With cellulose ester), t ₂ Mean flow time of solvent (sec), k=solvent constant (10 for 98/2wt/wt acetone/water), and c=concentration (0.200 g/dL).

Cellulose acetate is typically present in the polymer composition in an amount greater than about 15wt%, such as an amount greater than about 25wt%, such as an amount greater than about 35wt%, such as an amount greater than about 45wt%, such as an amount greater than about 55%. Cellulose acetate is typically present in the polymer composition in an amount of less than about 85wt%, such as in an amount of less than about 80wt%, such as in an amount of less than about 75wt%, such as in an amount of less than about 70wt%, such as in an amount of less than about 65 wt%.

In accordance with the present disclosure, cellulose ester polymers are combined with one or more biodegradable fillers and one or more plasticizers. As mentioned above, biodegradable fillers typically include monosaccharides, monosaccharide esters, polysaccharides, polysaccharide esters, or mixtures thereof. In one aspect, biodegradable fillers are selected that degrade at a greater rate than the cellulose ester polymer. Some fillers, such as starch, glucose or dextran, may also serve as food sources for various microorganisms. Thus, these fillers also further accelerate the degradation of the polymer once it has entered the solid waste stream. One or more biodegradable fillers may also be selected to improve one or more mechanical properties. Furthermore, combinations of different fillers may be used to take full advantage of the different properties and performance of polymer articles made from the polymer compositions. For example, dextran or starch may be included in the polymer composition to improve degradation, while cellulosic fibers (e.g., hemp or cork fibers) are included in the polymer composition to increase strength or improve other mechanical properties.

Biodegradable fillers for use in the present disclosure may take various forms. For example, in one aspect, the biodegradable filler may be in powder form or in particulate form. Alternatively, the filler may be in the form of fibers. The fibers may have a relatively short length, or may have a relatively long length. For example, fibers having a length of about 0.1mm to about 5mm, such as about 0.8mm to about 2.5mm, may be used. In other embodiments, the fibers may have a length of greater than about 5mm, such as greater than about 6mm, and typically less than about 12mm, such as less than about 10 mm.

As mentioned above, the biodegradable filler may be a monosaccharide. Suitable monosaccharides include glucose, sucrose, lactose, fructose, galactose, ribose, xylose, and mixtures thereof. The biodegradable filler may also be a polysaccharide or an ester thereof, including disaccharides and engineered polysaccharides. Polysaccharides that may be selected for use in the present disclosure include starches, celluloses (e.g., alpha-cellulose), hemicelluloses, hyaluronic acid compounds, alginates, guar gum, chitin, chondroitin, starches, modified starches, hydrolyzed starches, modified hydrolyzed starches, sisal, mucilage glue, dextran compounds, and polymers, including alpha-1, 3-glucan, hemp seeds, and the like.

Typically, the one or more biodegradable fillers may be included in the polymer composition in an amount of about 0.1wt% to about 95wt% (including all increments of 1wt% therebetween). For example, the one or more biodegradable fillers may be included in the polymer composition in an amount of greater than about 1wt%, such as an amount of greater than about 3wt%, such as an amount of greater than about 5wt%, such as an amount of greater than about 7wt%, such as an amount of greater than about 10wt%, such as an amount of greater than about 12wt%, such as an amount of greater than about 15wt%, such as an amount of greater than about 17wt%, such as an amount of greater than about 20wt%, such as an amount of greater than about 22wt%, such as an amount of greater than about 25wt%, such as an amount of greater than about 27wt%, such as an amount of greater than about 30 wt%. The one or more biodegradable fillers are typically present in the polymer composition in an amount of less than about 80wt%, such as less than about 50wt%, such as less than about 40wt%, such as less than about 30 wt%.

The weight ratio of the cellulose acetate polymer to the one or more biodegradable fillers may generally be from about 1:99 to about 99:1. For example, the weight ratio of cellulose acetate to one or more biodegradable fillers may be from about 1:75 to about 75:1, such as from about 1:50 to about 50:1, such as from about 1:25 to about 25:1, such as from about 1:10 to about 10:1, such as from about 1:5 to about 5:1. In one aspect, the cellulose acetate is present in an amount greater than the biodegradable filler. For example, the weight ratio between the cellulose acetate and the one or more biodegradable fillers may be at least about 1.5:1, such as at least about 2:1, such as at least about 3:1, such as at least about 5:1, such as at least about 10:1.

In addition to one or more biodegradable fillers, cellulose acetate is also combined with one or more plasticizers. Plasticizers particularly suitable for use in the polymer composition include glyceryl triacetate, glyceryl monoacetate, glyceryl diacetate, and mixtures thereof. Other suitable plasticizers include tris (chloroisopropyl) phosphate, tris (2-chloro-1-methylethyl) phosphate, triethyl citrate, acetyl triethyl citrate, glycerol, or mixtures thereof.

Other examples of plasticizers include, but are not limited to, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, acetyl tributyl citrate, tributyl ortho acetyl citrate, dibutyl tartrate, ethyl phthaloyl benzoate, N-ethyl toluene sulfonamide, ortho toluene p-toluenesulfonate, aromatic diols, substituted aromatic diols, aromatic ethers, glycerol tripropionate, triphenyl essence, glycerol, glyceride, glycerol tribenzoate, glycerol acetate benzoate, polyethylene glycol esters, polyethylene glycol diesters, di-2-ethylhexyl polyethylene glycol esters, glycerol esters, diethylene glycol, polypropylene glycol, polyethylene glycol diglycidyl ether, dimethyl sulfoxide, N-methyl pyrrolidone, propylene carbonate, C ₁ -C ₂₀ Dicarboxylic acid esters, dimethyl adipate (and other dialkyl esters), dibutyl maleate, dioctyl maleate, resorcinol monoacetate, catechol esters, phenols, epoxidized soybean oil, castor oil, linseed oil, epoxidized linseed oil, other vegetable oils, other seed oils, difunctional glycidyl ethers based on polyethylene glycols, alkyl lactones (e.g., gamma valerolactone), alkyl phosphates, aryl phosphates, phospholipids, fragrances (including some described herein, such as eugenol, cinnamyl alcohol, camphor, methoxyhydroxyacetophenone (vanillyl ketone), vanillin and ethyl vanillin), 2-phenoxyethanol, glycol ethers, glycol esters, glycol ester ethers, polyglycol esters, glycol ethers, propylene glycol ethers, glycol esters (e.g., ethylene glycol diacetate), propylene glycol esters, polypropylene glycol esters, acetylsalicylic acid, acetaminophen, naproxen, imidazole, triethanolamine, benzoic acid, benzyl benzoate, salicylic acid, 4-hydroxybenzoic acidPropyl-4-hydroxybenzoate, methyl-4-hydroxybenzoate, ethyl-4-hydroxybenzoate, benzyl-4-hydroxybenzoate, glycerol tribenzoate, neopentyl dibenzoate, triethylene glycol dibenzoate, trimethylolethane tribenzoate, butylhydroxytoluene, butylhydroxyanisole, sorbitol, xylitol, ethylenediamine, piperidine, piperazine, hexamethylenediamine, triazine, triazole, pyrrole, and the like, any derivatives thereof, and any combination thereof.

In one aspect, carbonates may be used as plasticizers. Exemplary carbonates may include, but are not limited to, propylene carbonate, butylene carbonate, diphenyl carbonate, phenyl methyl carbonate, xylene carbonate, glycerol carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, isopropyl phenyl 2-ethylhexyl carbonate, isopropyl phenyl isodecyl carbonate, isopropyl phenyl tridecyl carbonate, and the like, and any combination thereof.

In yet another aspect, the plasticizer may be a polyol benzoate. Exemplary polyol benzoates may include, but are not limited to, glycerol tribenzoate, propylene glycol dibenzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, sucrose benzoate, polyethylene glycol dibenzoate, neopentyl glycol dibenzoate, trimethylol propane tribenzoate, trimethylol ethane tribenzoate, pentaerythritol tetrabenzoate, sucrose benzoate (degree of substitution 1 to 8), and combinations thereof. In some cases, a tribenzoate (e.g., a glycerol tribenzoate) may be preferred. In some cases, the polyol benzoate may be solid at 25 ℃ and less than 0.05g/100mL water soluble at 25 ℃.

Plasticizers may also be biobased. For example, the use of a bio-based plasticizer may render the polymer composition suitable for contact with food products. Biobased plasticizers particularly suitable for use in the compositions of the present disclosure include alkyl ketal esters, non-petroleum hydrocarbon esters, biobased polymers or oligomers (having a number average molecular weight of 1000 or less), such as polycaprolactone, or mixtures thereof.

In one aspect, the bio-based plasticizer is an alkyl ketal ester having a chemical structure corresponding to structure I as provided below:

wherein a is 0 to 12; b is 0 or 1; each R ¹ Independently hydrogen, hydrocarbyl or substituted hydrocarbyl; each R ² 、R ³ And R is ⁴ Independently methylene, alkylmethylene, or dialkylmethylene, x is at least 1, y is 0 or a positive number, and x+y is at least 2; r is R ⁶ Is hydrocarbyl or substituted hydrocarbyl, and each Z is independently-O-, -NH-or-NR-, wherein R is a hydrocarbyl or substituted hydrocarbyl group.

The plasticizers described above correspond to the reaction products of polyols, amino alcohols or polyamines with certain 1, 2-and/or 1, 3-alkanediol ketals of oxo-carboxylic esters. The 1, 2-and 1, 3-alkanediol ketals of the oxo-carboxylic acid esters are referred to herein as "alkyl ketal esters". Up to 1 mole of the alkyl ketal ester can be reacted with each equivalent of hydroxyl or amino groups provided by the polyol, amino alcohol, or polyamine. The polyol, amino alcohol or polyamine is most preferably difunctional, but polyols, amino alcohols and polyamines having more than two hydroxyl and/or amino groups may be used.

The values of x and y in structure I depend on the number of hydroxyl or amino groups of the polyol, amino alcohol or polyamine, the number of moles of alkyl ketal ester per mole of polyol, amino alcohol or polyamine, and the degree of reaction completion. The greater the amount of alkyl ketal ester, the lower the y value and the higher the x value.

In structure I, y is in particular 0 to 2, and x is in particular at least 2. All a in structure I are in particular from 2 to 12, more particularly from 2 to 10, more particularly from 2 to 8, more particularly from 2 to 6, more particularly from 2 to 4, and more particularly 2. All R ¹ In particular alkyl, in particular methyl. In some embodiments of structure I, all Z are-O-, y is 0, and x is 2; these products correspond to the reaction of 2 moles of alkyl ketal ester with 1 mole of diol. In the other oneIn some embodiments, all Z are-O-, y is 1, and x is 1; these products correspond to the reaction of 1 mole of alkyl ketal ester with 1 mole of diol.

In one embodiment, all b are 0. In another embodiment, all b are 1.

Some specific compounds according to structure I include those having the following structure:

in particular, wherein R ⁶ Is- (CH) ₂ )- _m Wherein m is 2 to 18, in particular 2,3,4 or 6. In a particular embodiment, R ⁶ Corresponding to 1, 4-butanediol, the residue after removal of the hydroxyl group, to give the structure (Ia)

In another particular embodiment, R ⁶ Corresponding to the residue after removal of the hydroxyl group of diethylene glycol, the structure (Ib) is obtained

In yet another particular embodiment, R ⁶ Corresponding to the residue of 2-methyl-1, 3-propanediol after removal of the hydroxyl group, to give Structure (Ic)

The compounds according to structure I may be prepared in transesterification or ester ammonolysis reactions between the corresponding polyol, amino alcohol or polyamine and the corresponding alkyl ketal ester. Alternatively, compounds according to structure I may be prepared by: the oxo-carboxylic acid is reacted with a polyol, amino alcohol or polyamine to form an ester or amide, and the resulting product is then ketalized with a 1, 2-or 1, 3-alkanediol (e.g., ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 2-pentanediol, 1, 3-pentanediol, 1, 2-hexanediol, 1, 3-hexanediol, etc.).

Alkyl ketal ester plasticizers are particularly suitable for use in combination with one or more other plasticizers. For example, in one aspect, the alkyl ketal ester plasticizer can be combined with a benzoate. The weight ratio between the two plasticizers can vary, such as from about 1:10 to about 10:1, such as from about 1:4 to about 4:1.

Another biobased plasticizer that may be incorporated into the polymer compositions of the present disclosure is a non-petroleum hydrocarbon ester. For example, one example is a non-petroleum hydrocarbon ester sold under the trade name HALLGREEN by Hall Star corporation of Illinois, chicago. The non-petroleum hydrocarbon ester plasticizer may comprise, for example, a biobased content of greater than about 50wt%, such as greater than about 70wt%, such as greater than about 99wt%. For example, esters are derived primarily from agricultural, forestry or marine materials and are therefore biodegradable. In one aspect, the non-petroleum hydrocarbon ester plasticizer has a specific gravity of about 1.16 or greater, such as about 1.165 or greater, such as about 1.17 or greater, such as about 1.74 or greater, and typically about 1.19 or less, such as about 1.185 or less, such as about 1.18 or less, such as about 1.78 or less, at 25 ℃. The acid value of the non-petroleum hydrocarbon ester plasticizer is from about 0.5mgKOH/g to about 0.6mgKOH/g, such as from about 0.53mgKOH/g to about 0.57mgKOH/g.

In another aspect, the polymer composition comprises a biobased plasticizer that is a biobased polyester, such as a biobased aliphatic polyester having a relatively low molecular weight. For example, the plasticizer may comprise a bio-based polyester polymer having a number average molecular weight of less than about 1000, such as less than about 900, such as less than about 800, and typically greater than about 500. In one embodiment, the bio-based plasticizer is a polycaprolactone having a number average molecular weight of 1000 or less. Alternatively, the bio-based plasticizer may be a polyhydroxyalkanoate having a number average molecular weight of 1000 or less.

In one aspect, the plasticizer is phthalate-free. In fact, the polymer composition may be formulated to be phthalate-free. For example, the phthalate may be present in the polymer composition in an amount of about 0.5% or less, such as about 0.1% or less.

Typically, the one or more plasticizers may be present in the polymer composition in an amount of about 8wt% to about 40wt%, such as about 12wt% to about 35 wt%. In one aspect, the one or more plasticizers may be present in the polymer composition in an amount of about 19% or less, such as in an amount of about 17% or less, in an amount of about 15% or less, and in an amount of about 13% or less, such as in an amount of about 10% or less. The one or more plasticizers are typically present in an amount of about 5% or more, such as about 10% or more.

The cellulose acetate may be present relative to the plasticizer such that the weight ratio of cellulose acetate to one or more plasticizers is from about 60:40 to about 85:15, such as from about 70:30 to about 80:20. In one embodiment, the weight ratio of cellulose acetate to plasticizer is about 75:25.

In addition to the cellulose ester polymer, the one or more biodegradable fillers, and the one or more plasticizers, the polymer composition may contain various other additives and ingredients. For example, the polymer composition may include one or more acid scavengers that may be used to reduce acid emissions (e.g., acetic acid emissions). Suitable acid scavengers include alkali metal salts, alkaline earth metal salts, carbonates, oxides, hydroxides, amines or mixtures thereof. Specific acid scavengers include zinc oxide, magnesium oxide, calcium carbonate, sodium aluminum carbonate, aluminum silicate, aluminum magnesium carbonate, and mixtures thereof. The one or more acid scavengers may be present in the polymer composition in an amount of about 0.1wt% to about 5wt%, such as about 0.3wt% to about 2 wt%.

In addition to the acid agents described above, the polymer composition may also include a taste masking agent. For example, the taste masking agent may absorb odors and/or produce its own odors. Taste masking agents that may be incorporated into the composition include zeolites, particularly synthetic zeolites, perfumes, and the like.

Other additives and ingredients that may be included in the polymer composition include antioxidants, pigments, lubricants, softeners, antibacterial agents, antifungal agents, preservatives, flame retardants, and combinations thereof. Each of the above additives may generally be present in the polymer composition in an amount of about 5% or less, such as about 2% or less, and generally in an amount of about 0.1% or more, such as about 0.3% or more.

In some embodiments, flame retardants suitable for use in combination with the cellulose ester plastics described herein may include, but are not limited to, silica, metal oxides, phosphates, catechol phosphates, resorcinol phosphates, borates, inorganic hydrates, aromatic polyhalides, and the like, and any combination thereof.

In some embodiments, antifungal and/or antibacterial agents suitable for use in combination with the cellulose ester plastics described herein may include, but are not limited to, polyene antifungal agents (e.g., natamycin, clarithromycin, filipin, nystatin, amphotericin B, candicidin, and haramycin); imidazole antifungals, e.g. miconazole (available from WellSpring pharmaceutical Co., ltdObtained from McNeil Consumer healthcare Co., ltd.), ketoconazoleCommercially available), clotrimazole (available from Merck +.>And LOTRAMIN->From BayerCommercially available), econazole, omoconazole, bifonazole, butoconazole, fenticonazole, isoconazole, oxiconazole, sertaconazole (available from OrthoDematologics in->Commercially available), tioconazole and tioconazole; triazole antifungal agents (e.g., fluconazole, itraconazole, isaconazole, raffmonazole, posaconazole)Voriconazole, terconazole and albaconazole); thiazole antifungal agents (e.g., abafungin); allylamine antifungal agents (e.g., terbinafine (available from Novartis consumer healthcare company +.>Commercially available), naftifine (available from Merz in +.>Commercially available) and butenafine (available from Merck as LOTRAMIN +.>Commercially available); echinocandin antifungal agents (e.g., anidulafungin, caspofungin, and micafungin); polygonum tinctorium dialdehyde; benzoic acid; ciclopirox; tolnaftate (e.g., available from MDS consumer care company in +.>Commercial). Undecylenic acid; fluorocytosine; 5-fluorocytosine; griseofulvin; chlorpropyne-iodine; octanoic acid; and any combination thereof.

In some embodiments, preservatives suitable for use in combination with the cellulose ester plastics described herein may include, but are not limited to, benzoates, parabens (e.g., propyl-4-hydroxybenzoate series), and the like, as well as any combination thereof.

In some embodiments, pigments and dyes suitable for use in combination with the cellulose ester plastics described herein may include, but are not limited to, vegetable dyes, titanium dioxide, silicon dioxide, lemon yellow, E102, phthalocyanine blue, phthalocyanine green, quinacridone, perylene tetracarboxylic diimide, dioxazine, pyrenone (perinones) disazo dyes, anthraquinone dyes, carbon black, metal powders, iron oxide, ultramarine, calcium carbonate, kaolin, aluminum hydroxide, barium sulfate, zinc oxide, aluminum oxide, liquid and/or particulate formsDyes (cationic dyes, available from Clariant Se)rdevices obtained) (e.g.)>Bright yellow K-6G liquid, < >>Yellow K-4GL liquid, < >>Yellow K-GL liquid, ">Orange K-3GL liquid, < >>Bright red K-2GL liquid, < >>Red K-3BN liquid,Blue K-5R liquid, < >>Blue K-RL liquid, < >>Bluish green K-RL liquid/particles, +.>Brown K-BL liquid),>dyes (color aids available from BASF) (e.g., yellow 3GL, fastusol C Blue 74L), and the like, any derivatives thereof, and any combinations thereof.

In some embodiments, pigments and dyes suitable for use in combination with the cellulose ester plastics described herein may be food grade pigments and dyes. In some embodiments, examples of food grade pigments and dyes may include, but are not limited to, vegetable dyes, titanium dioxide, and the like, and any combination thereof.

In some embodiments, the antioxidants can reduce the oxidative and/or chemical degradation of the cellulose ester plastics described herein during storage, transportation, and/or application. In some embodiments, antioxidants suitable for use in combination with the cellulose ester plastics described herein may include, but are not limited to, anthocyanins, ascorbic acid, glutathione, lipoic acid, uric acid, resveratrol, flavonoids, carotenes (e.g., beta-carotene), carotenoids, tocopherols (e.g., alpha-tocopherol, beta-tocopherol, gamma-tocopherol, and delta-tocopherol), tocotrienols, tocopheryl acetate (e.g., tocopheryl acetate), panthenol, gallic acid, melatonin, aromatic secondary amines, benzofuranones, hindered phenols, polyphenols, hindered amines, organophosphorus compounds, thioesters, benzoates, lactones, hydroxylamine, butylhydroxytoluene ("BHT"), butylhydroxyanisole ("BHA"), hydroquinone, and the like, and any combination thereof.

In some embodiments, an antioxidant suitable for use in combination with the cellulose ester plastics described herein may be a food grade antioxidant. In some embodiments, examples of food grade antioxidants can include, but are not limited to, ascorbic acid, vitamin a, tocopherol, tocopheryl esters, beta-carotene, flavonoids, BHT, BHA, hydroquinone, and the like, and any combination thereof.

In another aspect, the polymer composition may comprise one or more blowing agents or foaming agents. For example, the polymer composition may be in the form of a foam, or may form a foam during the production of the polymer article.

The polymer compositions of the present disclosure may be formed into any suitable polymer article using any technique known in the art. For example, the polymeric article may be formed from the polymeric composition by extrusion molding, injection molding, blow molding, and the like.

Various methods for producing a composite polymer according to the present disclosure are described, for example, in U.S. patent publication nos. 2016/0201266, 2013/0276670, 2013/0210965, 2013/0210964, 2013/0207302, 2013/0207297, 2013/0207295, 2013/0206037, 2013/0206036, and 2013/0206035, all of which are incorporated herein by reference.

In one aspect, the polymer composition comprising cellulose acetate may be formulated such that the polymer composition has properties very similar to petroleum-based polymers (e.g., polypropylene). By matching the physical properties of petroleum-based polymers, the polymer compositions of the present disclosure are well suited for replacing those polymers in many different end-use applications.

Polymeric articles that may be made according to the present disclosure include drinking straws, beverage holders, automotive parts, knobs, door handles, household appliance parts, and the like.

For example, referring to FIG. 1, a straw 10 that may be made in accordance with the present disclosure is shown. In the past, pipettes have typically been made from petroleum-based polymers such as polypropylene. However, the cellulose acetate polymer compositions of the present disclosure may be formulated to match the physical properties of polypropylene. Thus, the straw 10 may be produced in accordance with the present disclosure and be entirely biodegradable.

Referring to fig. 2, a cup or beverage holder 20 is shown that may also be made in accordance with the present disclosure. For example, the cup 20 may be manufactured using injection molding or by any suitable thermoforming process. As shown in fig. 7, the lid 22 of the cup 20 may likewise be made of the polymer composition of the present disclosure. The lid may include a pouring spout 24 for dispensing beverage from the cup 20. In addition to lids for beverage holders, the polymer compositions of the present disclosure may be used to manufacture lids for all different types of containers, including food containers, packaging containers, storage containers, and the like.

In yet another embodiment, the polymer composition may be used to produce a hot beverage can 30 as shown in fig. 3. In addition to beverage cans 30, the polymer composition can also be used to produce plastic bottles 40 that can be used as water bottles or other sports beverage containers as shown in fig. 4.

Referring to fig. 5, an automobile interior is shown. The interior of an automobile includes various automobile parts that can be manufactured according to the present disclosure. For example, the polymer composition may be used to produce an automotive part 50 that includes at least a portion of an interior door handle. The polymer composition may also be used to produce parts on steering columns, such as automotive parts 60. In general, the polymer composition may be used to mold any suitable decorative trim or bezel, such as trim 70. In addition, the polymer composition can be used to produce knobs or handles that can be used in vehicle interiors.

The polymer composition is also very suitable for the production of cutlery such as forks, spoons and knives. For example, referring to fig. 6, disposable cutlery 80 is shown. Cutlery 80 comprises knife 82, fork 84, and spoon 86.

In yet another embodiment, the polymer composition may be used to produce a storage container 90 as shown in FIG. 8. The storage container 90 may include a lid 94 that mates with and engages the rim of the bottom 92. The bottom 92 may define an interior volume for containing items. The container 90 may be used to hold food or dry goods.

In still other embodiments, the polymer composition may be formulated to produce a paper tray pad, an eyeglass frame, a screwdriver handle, or any other suitable part.

These and other modifications and variations to the present disclosure may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present disclosure, which is more particularly set forth in the appended claims. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the application so further described in such appended claims.

Claims (24)

1. A polymer composition comprising:

a cellulose ester polymer;

a plasticizer comprising acetylglycerol; and

a biodegradable filler comprising a monosaccharide, a monosaccharide ester, a polysaccharide ester, or a mixture thereof.

2. The polymer composition of claim 1, wherein the biodegradable filler comprises fibers.

3. The polymer composition of claim 1, wherein the biodegradable filler comprises a powder or a particle.

4. The polymer composition according to any of the preceding claims, wherein the biodegradable filler comprises dextran, starch, modified starch, hydrolyzed starch, modified hydrolyzed starch, alpha-1, 3-glucan or a mixture thereof.

5. The polymer composition of claim 1, wherein the biodegradable filler comprises bast fibers.

6. The polymer composition of claim 5, wherein the bast fiber comprises hemp.

7. The polymer composition of claim 1, wherein the biodegradable filler comprises cellulose fibers, sisal fibers, viscose fibers, or a mixture thereof.

8. The polymer composition of claim 7, wherein the cellulosic fibers comprise hardwood fibers, softwood fibers, or a mixture thereof.

9. The polymer composition of claim 1, wherein the biodegradable filler comprises alpha-cellulose or an engineered polysaccharide.

10. The polymer composition of any of the preceding claims, wherein the one or more biodegradable fillers are present in the polymer composition in an amount of about 0.1wt% to about 75 wt%.

11. The polymer composition of any one of claims 1 to 9, wherein the one or more biodegradable fillers are present in the polymer composition in an amount of about 3wt% to about 50 wt%.

12. The polymer composition of any one of claims 1 to 9, wherein the one or more biodegradable fillers are present in the polymer composition in an amount of about 3wt% to about 25 wt%.

13. The polymer composition of any of the preceding claims, wherein the cellulose ester polymer comprises cellulose acetate having a degree of substitution of about 1.3 to about 2.4.

14. The polymer composition according to any of the preceding claims, wherein the polymer composition further comprises an acid scavenger.

15. A polymer composition according to any preceding claim wherein the plasticiser comprises monoacetin, diacetin, triacetin or a mixture thereof.

16. The polymer composition of any of the preceding claims, wherein the cellulose ester polymer is present in the polymer composition in an amount of about 15wt% to about 85wt%, such as about 55wt% to about 80wt%, and the plasticizer is present in the polymer composition in an amount of about 8wt% to about 40wt%, such as about 12wt% to about 35 wt%.

17. The polymer composition of any of the preceding claims, wherein the cellulose acetate consists essentially of cellulose diacetate.

18. The polymer composition of any of the preceding claims, wherein a second plasticizer is present, the second plasticizer comprising tris (chloroisopropyl) phosphate, tris (2-chloro-1-methylethyl) phosphate, triethyl citrate, acetyl triethyl citrate, glycerol, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, ethylAcyl tributyl citrate, tributyl ortho acetyl citrate, dibutyl tartrate, ethyl o-benzoylbenzoate, N-ethyltoluene sulfonamide, o-toluene p-toluene sulfonate, aromatic diols, substituted aromatic diols, aromatic ethers, glycerol tripropionate, triphenyl essence, glycerol, glyceride, glycerol tribenzoate, glycerol acetate benzoate, polyethylene glycol ester, polyethylene glycol diester, di-2-ethylhexyl polyethylene glycol ester, glyceride, diethylene glycol, polypropylene glycol, polyethylene glycol diglycidyl ether, dimethyl sulfoxide, N-methylpyrrolidone, propylene carbonate, C ₁ -C ₂₀ Dicarboxylic acid esters, dimethyl adipate, dibutyl maleate, dioctyl maleate, resorcinol monoacetate, catechol esters, phenol, epoxysoybean oil, castor oil, linseed oil, epoxylinseed oil, difunctional glycidyl ethers based on polyethylene glycol, alkyl lactones, alkyl phosphates, aryl phosphates, phospholipids, eugenol, cinnamyl alcohol, camphor, methoxyhydroxyacetophenone, vanillin, 2-phenoxyethanol, glycol ethers, glycol esters, glycol ester ethers, polyglycol esters, glycol ethers, propylene glycol ethers, glycol esters, propylene glycol esters, polypropylene glycol esters, acetylsalicylic acid, acetaminophen, napthoic acid, imidazole, triethanolamine, benzoic acid, benzyl benzoate, salicylic acid, 4-hydroxybenzoic acid, propyl-4-hydroxybenzoate, methyl-4-hydroxybenzoate, ethyl-4-hydroxybenzoate, benzyl-4-hydroxybenzoate, glyceryl tribenzoate, neopentyl dibenzoate, triethylene glycol dibenzoate, trimethylolethane tribenzoate, butylhydroxytoluene, butyloxybenzol, sorbitol, ethylene diamine, piperazine, pyrrole, any combination thereof, and derivatives thereof.

19. An article made from the polymer composition of any of the preceding claims.

20. The article of claim 19, wherein the article is a beverage holder, straw, hot beverage can, fork, knife, spoon, packaging material, container, lid, or automotive interior trim.

21. The polymer composition of any one of claims 1 to 18, wherein the polymer composition is in the form of extruded pellets.

22. The article of claim 19, wherein the article is formed by injection molding or extrusion.

23. The article of claim 19, wherein the article comprises an extruded film.

24. The polymer composition of any one of claims 1 to 18, wherein the polymer composition comprises a foam.